Competitive tetrel bond and hydrogen bond in benzaldehyde–CO2: characterization via rotational spectroscopy
| Autor: | Hao Wang, Xuefang Xu, Xiao Tian, Xiujuan Wang, Daniel A Obenchain, Wanying Cheng, Qian Gou, Yang Zheng |
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| Rok vydání: | 2021 |
| Předmět: |
Quantum chemical
education.field_of_study Hydrogen bond Bond Population General Physics and Astronomy 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Characterization (materials science) Benzaldehyde chemistry.chemical_compound Crystallography chemistry Rotational spectroscopy Physical and Theoretical Chemistry 0210 nano-technology education Natural bond orbital |
| Zdroj: | Physical Chemistry Chemical Physics. 23:25784-25788 |
| ISSN: | 1463-9084 1463-9076 |
| Popis: | The rotational spectrum of the 1:1 benzaldehyde-CO2 complex has been investigated by pulsed-jet Fourier transform microwave spectroscopy complemented with quantum chemical calculations. Two isomers, both characterized by one C···O tetrel bond (n → π* interaction) and one C-H···O hydrogen bond (n → σ* interaction), have been observed in the pulsed jet. Competition between tetrel bond and hydrogen bond has been disclosed by natural bond orbital analysis: Isomer I is characterized by one dominating CCO2···O tetrel bond (12.6 kJ mol-1) and a secondary (C-H)formyl···O hydrogen bond (2.2 kJ mol-1). On the contrary, the (C-H)···O hydrogen bond (7.6 kJ mol-1) becomes the dominant one in isomer II, while the CCO2···O tetrel bond (5.8 kJ mol-1) becomes much weaker with respect to that of isomer I. The relative population ratio of the two isomers was estimated to be NI/NII ≈ 2/1 by intensity measurements. |
| Databáze: | OpenAIRE |
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